A negative dispersion compound containing a carbonate group, and its preparation and application

Abstract

The present invention discloses a negative dispersion compound containing a carbonate group, its preparation and application, belonging to the technical field of optical materials. The negative dispersion compound containing a carbonate group is selected from the compounds represented by the general formula (1). For the negative dispersion compound containing a carbonate group of the present invention, due to the presence of the carbonate group, the damp heat durability life of the film is effectively improved, and the negative dispersion compound containing a carbonate group can be applied to negative dispersion optical film materials.

Description

Technical Field

[0001] The present invention relates to a negative dispersion compound containing a carbonate group and its preparation and application, belonging to the technical field of optical materials. Background Art

[0002] A polymerizable compound (RM) is a raw material for preparing various optically anisotropic bodies. Usually, an RM solution is coated on a substrate and aligned, and after curing, an optically anisotropic polymer film with a uniform orientation, that is, an optically anisotropic body, is formed. The orientation of the film can be planar (liquid crystal molecules are basically parallel to the layer orientation), vertical (rectangular or perpendicular to the layer), or inclined, or it can be a cholesteric phase orientation. Therefore, polymerizable compound materials have received extensive attention.

[0003] According to different application fields, optically anisotropic bodies include, but are not limited to, birefringent films, optical retardation films (phase difference films), negative dispersion optical films, optical compensation films, visual expansion films, reflection films, selective reflection films, antireflection films, brightness enhancement films, liquid crystal alignment films, polarizing films (deflection plates), polarizing elements, circular polarizing elements, elliptical polarizing elements, and various other optical elements.

[0004] Polymerizable compound materials control optical anisotropy by optically compensating for the dispersion generated due to different wavelengths during the propagation of light in a medium, improve optical efficiency, and increase the viewing angle. However, the damp heat durability of the films prepared from existing polymerizable compound materials is still not satisfactory.

[0005] Therefore, it is required to develop the following negative dispersion compound containing a carbonate group and its synthesis method and application, so as to solve the above technical problems. Summary of the Invention

[0006] At least aiming at one of the problems existing in the above prior art, the present invention provides a negative dispersion compound containing a carbonate group and its preparation. Due to the carbonate group, the damp heat durability life of the film is effectively improved. The negative dispersion compound containing a carbonate group can be applied to negative dispersion optical film materials.

[0007] To achieve the above object, the present invention adopts the following technical solution: A polymerizable compound, wherein the polymerizable compound is a negative dispersion compound containing a carbonate group.

[0008] The dispersion compound containing a carbonate group is selected from the compounds represented by the general formula (1),

[0009] (1); In the compound of the general formula (1), L1 and L2 each independently represent a single bond or an alkylene group having 1 to 30 carbon atoms; one or more -CH2- in the alkylene group may be substituted by -O-, -S-, -NH-, -CO-, -OCO-, -COO-, -SCO-, -COS-; P1 represents a polymerizable group.

[0010] Preferably, the polymerizable group P1 is selected from the groups represented by the general formula P-1, general formula P-2, general formula P-3, general formula P-4, general formula P-5, general formula P-6, general formula P-7, general formula P-8, general formula P-9, general formula P-10, general formula P-11 or general formula P-12;

[0011] ;

[0012] In the formula, each R3 independently represents a hydrogen atom, a halogen, a cyano group, a hydroxyl group, a nitro group, a carboxyl group, a carbamoyloxy group, an amino group, a sulfamoyl group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thiocyanato group, a cyano group, an alkyl group having 1 to 30 carbon atoms, a halogenated alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, a halogenated alkoxy group having 1 to 30 carbon atoms, an alkoxycarbonyl group having 1 to 30 carbon atoms, a halogenated alkoxycarbonyl group having 1 to 30 carbon atoms, an alkylcarbonyl group having 1 to 30 carbon atoms, a halogenated alkylcarbonyl group having 1 to 30 carbon atoms, an alkylacyloxy group having 1 to 30 carbon atoms, a halogenated alkylacyloxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, a halogenated alkenyl group having 2 to 30 carbon atoms, an alkenyloxy group having 2 to 30 carbon atoms or a halogenated alkenyloxy group having 2 to 30 carbon atoms.

[0013] Preferably, the polymerizable group represented by P1 is selected from the group represented by the general formula P-1.

[0014] Preferably, R3 represents a hydrogen atom.

[0015] Preferably, L1 and L2 each independently represent an alkylene group having 1 to 30 carbon atoms.

[0016] Preferably, the general formula (1) of the negative dispersion compound containing a carbonate group is selected from the general formula T-1, general formula T-2 or general formula T-3, and the general formula T-1, general formula T-2 and general formula T-3 are as follows:

[0017] T-1;

[0018] T-2;

[0019] T-3.

[0020] The present invention also provides a polymerizable compound composition, comprising the polymerizable compound of the above general formula (1) and at least one additional polymerizable compound.

[0021] Preferably, the additional polymerizable compound is selected from one or more of the compounds represented by general formula M-1, general formula M-2 or general formula M-3; the general formula M-1, general formula M-2 or general formula M-3 is as follows:

[0022] ;

[0023] ;

[0024] .

[0025] Preferably, in the polymerizable compound composition, the additional polymerizable compound comprises the compound of general formula M-1, general formula M-2 and general formula M-3.

[0026] Preferably, the additional polymerizable compound, by weight percentage, comprises 50% of the compound of general formula M-1, 30% of the compound of general formula M-2 and 20% of the compound of general formula M-3.

[0027] Preferably, in the polymerizable compound composition, the addition concentration of the polymerizable compound of general formula (1) in the polymerizable compound composition is not less than 30 wt%.

[0028] Preferably, in the polymerizable compound composition, the addition concentration of the polymerizable compound of general formula (1) in the polymerizable compound composition is not less than 40 wt%.

[0029] Preferably, in the polymerizable compound composition, the addition concentration of the polymerizable compound of general formula (1) in the polymerizable compound composition is not less than 50 wt%.

[0030] Preferably, in the polymerizable compound composition, the addition concentration of the polymerizable compound of general formula (1) in the polymerizable compound composition is not less than 60 wt%.

[0031] Preferably, the polymerizable compound composition further comprises an additive.

[0032] Preferably, the additive includes, but is not limited to, polymerization initiator, sensitizer, sensitizer, stabilizer, leveling agent, surfactant, inhibitor, antioxidant, colorant, dispersant, lubricant, hydrophobic agent, binder, flow improver, defoamer, degassing agent, diluent, thixotropic agent, gelling agent, catalyst, metal, metal complex, luminescent material, etc.

[0033] Preferably, the content of the additive is 0.01 to 10 wt%, preferably 0.02 to 8 wt%, more preferably 0.05 to 5 wt%, and most preferably 0.1 to 3 wt%, based on the total weight of the polymerizable composition.

[0034] In another aspect, the present invention also provides a polymerizable compound composition solution, comprising the polymerizable compound composition described above and an organic solvent.

[0035] Preferably, the organic solvent has good solubility in the polymerizable compound composition and can be removed by drying below 100°C. The organic solvent includes, but is not limited to, those without special limitation, but preferably organic solvents in which the polymerizable compound shows good solubility, preferably aromatic solvents such as toluene, xylene, cumene, mesitylene; ester solvents such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone; ether solvents such as tetrahydrofuran, 1,2-dimethoxyethane, anisole; amide solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone; propylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, γ-butyrolactone, chlorobenzene, etc.

[0036] The organic solvents described above can be used alone or in combination of two or more.

[0037] For the consideration of solution stability, it is preferred to use one or more of ketone solvents, ether solvents, ester solvents and aromatic solvents.

[0038] Preferably, the organic solvent is selected from cyclopentanone.

[0039] Preferably, in the polymerizable compound composition solution, the content of the organic solvent is 30 to 95 wt%, preferably 40 to 90 wt%, more preferably 50 to 85 wt%, and most preferably 60 to 80 wt%, based on the total weight of the polymerizable composition solution.

[0040] When preparing the polymerizable compound composition solution, heating and / or stirring is advantageously carried out to promote the dissolution of the polymerizable compound composition.

[0041] In yet another aspect, the present invention also provides an optically anisotropic body, comprising a substrate and a polymer film formed by curing the polymerizable compound composition solution described above, and, if necessary, an alignment film.

[0042] Preferably, the substrate includes, but is not limited to, a glass substrate, a metal substrate, a ceramic substrate, a polymer substrate, which is a selection made according to the alignment film that is present as needed, and the polymer film formed by curing the polymerizable compound composition solution are stacked in sequence to form an optically anisotropic body.

[0043] Preferably, the polymer substrate is a substrate such as cellulose derivative, polyolefin, polyester, polyolefin, polycarbonate, polyacrylate, polyarylate, polyethersulfone, polyamide, polyimide, polyphenylene sulfide, polyphenylene ether or polystyrene.

[0044] Preferably, the polymer substrate is polyester, polystyrene, polyolefin, cellulose derivative, polyarylate, polycarbonate, which is based on the process applicability of the optically anisotropic body, especially considering heat resistance and chemical stability.

[0045] Preferably, the alignment film material includes, but is not limited to, materials such as polyimide, polysiloxane, polyamide, polyvinyl alcohol, polycarbonate, polystyrene, polyphenylene ether, polyarylate, polyethylene terephthalate, polyethersulfone, epoxy resin, acrylic resin, epoxy acrylate, coumarin, chalcone, cinnamate, anthraquinone, azo compound, aryl vinyl compound, etc.

[0046] Preferably, the alignment treatment of the alignment film is stretching treatment, rubbing treatment, polarized ultraviolet-visible light irradiation or ion beam treatment.

[0047] Preferably, the alignment treatment of the alignment film is rubbing treatment or polarized ultraviolet-visible light irradiation.

[0048] Preferably, the method for preparing the negative dispersion optical film material includes a coating method.

[0049] Preferably, the coating methods include applicator method, bar coating method, spin coating method, gravure printing method, flexographic printing method, inkjet method, die coating method, CAP coating method, dipping, etc., which are all well-known methods in the art.

[0050] Preferably, after coating the polymerizable composition solution, the negative dispersion optical film material is dried.

[0051] When polymerizing the polymerizable compound composition solution of the present invention, it is desirable to carry out the polymerization rapidly. Therefore, it is preferably polymerized by irradiating active energy rays such as ultraviolet-visible light or electron rays; when using ultraviolet-visible light, a polarized light source or a non-polarized light source can be used.

[0052] As the optically anisotropic body of the present invention, advantageously it is a birefringent film; the birefringent film of the present invention is made in the same way as the optically anisotropic body of the present invention.

[0053] The polymerizable compound provided by the present invention is a negative dispersion compound containing a carbonate group, which has good orientation. At the same time, due to the presence of the carbonate group in the negative dispersion compound, the lifespan of the film is effectively improved. The negative dispersion compound containing a carbonate group can be applied to the negative dispersion optical film material. Detailed implementation mode

[0054] The following is a clear and complete description of the technical solutions in the implementation of the present invention. The described embodiments are only a part of the embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of the present invention. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents, instruments, or components not specified by the manufacturer, they are all conventional products that can be obtained through commercial purchase.

[0055] The present invention provides a polymerizable compound represented by the general formula (1), and provides a polymerizable compound composition containing the compound, a resin, a resin additive, an oil, a color filter, an adhesive, an adhesive agent, a grease, an ink, a pharmaceutical, a cosmetic, a detergent, a building material, a packaging material, a liquid crystal material, an organic EL material, an organic semiconductor material, an electronic material, a display element, an electronic device, a communication device, an automotive part, an aircraft part, a mechanical part, a pesticide, and a food, as well as products using them, a polymerizable compound composition, a polymer obtained by polymerizing the polymerizable compound composition, and an optically anisotropic body using the polymer.

[0056] (1).

[0057] In order to improve the storage stability of the polymerizable compound composition of the present invention, a stabilizer may also be added thereto. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, benzenethiols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, etc. When using a stabilizer, the addition amount is preferably in the range of 0.005% by mass to 1% by mass, more preferably 0.02% by mass to 0.8% by mass, and further preferably 0.03% by mass to 0.5% by mass with respect to the composition.

[0058] In addition, when the polymerizable compound composition containing the compound of the present invention is used for applications such as films, optical elements, functional pigments, pharmaceuticals, cosmetics, coating agents, synthetic resins, etc., metals, metal complexes, dyes, pigments, colorants, fluorescent materials, phosphorescent materials, surfactants, leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, metal oxides such as titanium oxide, etc. may also be added according to the purpose.

[0059] The polymers obtained by polymerizing the polymerizable compound compositions containing the compounds of the present invention can be used for various purposes. For example, the polymers obtained by polymerizing the polymerizable compositions containing the compounds of the present invention without orientation can be used as light scattering plates, depolarizing plates, and anti-Moiré plates. In addition, the polymers obtained by polymerization after orientation have optical anisotropy and are useful. Such optically anisotropic bodies can be produced, for example, by the following method: a polymerizable compound composition containing the compounds of the present invention is supported on a substrate that has been subjected to rubbing treatment with cloth or the like, a substrate on which an organic film has been formed, or a substrate having an alignment film with obliquely evaporated SiO2, or is sandwiched between substrates, and then the polymerizable compound composition is polymerized.

[0060] Examples of the method for supporting the polymerizable compound composition on a substrate include spin coating, die coating, extrusion coating, roll coating, wire bar coating, gravure coating, spraying, dipping, printing, etc. In addition, when coating, an organic solvent can be added to the polymerizable compound composition. As the organic solvent, hydrocarbon solvents, halogenated hydrocarbon solvents, ether solvents, alcohol solvents, ketone solvents, ester solvents, aprotic solvents, etc. can be used. For example, as hydrocarbon solvents, toluene or hexane can be mentioned; as halogenated hydrocarbon solvents, chloromethane can be mentioned; as ether solvents, tetrahydrofuran, acetoxy-2-ethoxyethane, or ethylene glycol monomethyl ether acetate can be mentioned; as alcohol solvents, methanol, ethanol, or isopropanol can be mentioned; as ketone solvents, acetone, methyl ethyl ketone, cyclohexanone, γ-butyrolactone, or N-methylpyrrolidone can be mentioned; as ester solvents, ethyl acetate or cellosolve can be mentioned; as aprotic solvents, dimethylformamide or acetonitrile can be mentioned. These can be used alone or in combination, and can be appropriately selected considering their vapor pressures and the solubility of the polymerizable compound composition. As a method for volatilizing the added organic solvent, natural drying, heat drying, pressure drying, or pressure heat drying can be used. In order to further improve the coatability of the polymerizable liquid crystal material, it is also effective to provide an intermediate layer such as a polyimide film on the substrate or to add a leveling agent to the polymerizable liquid crystal material. The method of providing an intermediate layer such as a polyimide film on the substrate is effective for improving the adhesion between the polymer obtained by polymerizing the polymerizable material and the substrate.

[0061] As alignment treatments other than the above, alignment by the flow of a liquid crystal material, by an electric field, or by a magnetic field can be cited. These alignment means can be used alone or in combination. Further, as an alignment treatment method in place of rubbing, a photo-alignment method can also be used. As the shape of the substrate, in addition to a flat plate, a curved surface can also be included as a component. As the material constituting the substrate, organic materials and inorganic materials can be used without limitation. As organic materials that can be used as the substrate material, for example, polyethylene terephthalate, polycarbonate, polyimide, polyamide, polymethyl methacrylate, polystyrene, polyvinyl chloride, polytetrafluoroethylene, chlorotrifluoroethylene, polyarylate, polysulfone, triacetyl cellulose, cellulose, polyether ether ketone, etc. can be cited. In addition, as inorganic materials, for example, silicon, glass, calcite, etc. can be cited.

[0062] When polymerizing the polymerizable compound composition containing the compound of the present invention, since rapid polymerization is desired, a method of polymerizing it by irradiating active energy rays such as ultraviolet rays or electron rays is preferred. When using ultraviolet rays, a polarized light source or a non-polarized light source can be used. Further, when polymerizing in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency with respect to the active energy rays. In addition, the following means can also be used: after polymerizing only a specific part by using a mask during light irradiation, the alignment state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and then active energy rays are further irradiated to polymerize it. In addition, the temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the polymerizable compound composition of the present invention is maintained. In particular, when manufacturing an optically anisotropic body by photopolymerization, from the viewpoint of avoiding inducing undesired thermal polymerization, it is also preferred to polymerize it at a temperature as close to room temperature as possible, that is, typically at a temperature of 25 °C. The intensity of the active energy rays is preferably 0.1 mW / cm 2 ~2 W / cm 2 . When the intensity is 0.1 mW / cm 2 or less, a large amount of time is required to complete photopolymerization and the productivity deteriorates. When the intensity is 2 W / cm 2 or more, there is a risk of deterioration of the polymerizable compound or the polymerizable compound composition.

[0063] Regarding the optically anisotropic body obtained by polymerization, for the purpose of reducing initial property changes and exhibiting stable properties, heat treatment can also be carried out. The temperature of the heat treatment is preferably in the range of 50 to 250 °C, and the heat treatment time is preferably in the range of 30 s to 12 h.

[0064] The optically anisotropic body manufactured by such a method can be peeled off from the substrate and used as a monomer, or can be used without peeling. In addition, the obtained optically anisotropic bodies can be laminated, or can be used by bonding to other substrates.

[0065] Hereinafter, synthesis examples, examples and application examples are listed to further illustrate the present invention, but the present invention is not limited to these examples. Unless otherwise specified, the percentages in the raw materials and compositions are weight percentages.

[0066] Preparation of Example 1 T-1

[0067] The preparation method of T-1 is as follows:

[0068] Step 1, Preparation of Intermediate S-3: Add 25 g of S-1 into a 500 ml reaction flask, add 245 ml of DMF, lower the temperature to below 10 °C, protect with nitrogen, add 25 g of potassium tert-butoxide in batches. After completion, continue stirring for 1 h, then dropwise add 28 g of S-2. After the addition is complete, raise the temperature to 25 °C and react for 5 h; The reaction equation of Step 1 is as follows:

[0069] ;

[0070] Work-up: Lower the temperature, then add 350 g of dichloromethane, add 400 g of water, perform liquid-liquid extraction, wash once with 400 g of saturated brine, then wash once with 300 g of 10% brine, add sodium sulfate for drying, add 70 g of alumina and stir for 1 h, then pass through a 140 g alumina chromatography column, elute with 150 g of DCM, evaporate the eluate to obtain 45 g of a green oil. Crystallize with 40 g of dichloromethane and 40 g of petroleum ether at low temperature, filter by suction to obtain 28 g of a green solid S-3, and the yield is 69%;

[0071] Step 2, Preparation of Intermediate S-5: Add 25 g of S-4 into a 500 ml reaction flask, add 250 ml of dichloromethane, add 9 g of S-3, and add 1 g of camphorsulfonic acid. Protect with nitrogen, raise the temperature to 50 °C and react for 5 h to obtain S-5; The reaction equation of Step 2 is as follows:

[0072] ;

[0073] Without purification, it is directly used as the raw material for the next step. Due to its impurity, the yield of this step is converted to 100%;

[0074] Step 3: Preparation of Intermediate S-7: In a 1 L three-necked flask, add 110 g of S-6 and 162 g of N,N-dimethylaniline. Then add 500 g of dichloromethane. Cool the temperature to 0 °C, and dropwise add 75 g of triphosgene dissolved in 250 g of dichloromethane. After the addition is complete, raise the temperature to 25 °C and react for 4 h. Take a sample for derivatization and send it for HPLC testing. After passing the test, perform post-treatment: Lower the temperature, and dropwise add 320 g of 15% hydrochloric acid. Wash with water and separate the layers. Extract the aqueous phase once with 250 g of dichloromethane. Combine the organic phases, add 0.12 g of BHT, and then perform distillation under reduced pressure while heating to obtain 150 g of S-7 product, with a yield of 95%. The reaction equation for Step 3 is as follows:

[0075] ;

[0076] Step 4: Preparation of Intermediate T-1: Add 21 g of triethylamine to the reaction solution of S-5 under nitrogen protection. Cool the temperature to 0 °C, and dropwise add a dichloromethane solution of S-7 (32.7 g of S-7 dissolved in 50 g of dichloromethane). After the addition is complete, raise the temperature to 25 °C and react for 3 h. The reaction equation for Step 4 is as follows:

[0077] ;

[0078] For post-treatment, directly pass the reaction solution through a silica gel chromatography column, then concentrate it. Dissolve the oily substance with 30 g of dichloromethane, dropwise add 300 g of methanol, stir to crystallize, filter by suction, and dry to obtain 23 g of T-1 product, with a yield of 70%.

[0079] 1H NMR of product T-1 in this example: δ 1.30~1.32 (m, 6H), 1.45~1.47 (m, 6H), 1.51~1.54 (m, 8H), 1.58~1.61 (m, 4H), 1.78~1.82 (m, 14H), 1.88~1.90 (m, 8H), 2.44~2.45 (m, 2H), 3.92~3.94 (m, 4H), 4.00~4.02 (m, 8H), 4.14~4.16 (m, 6H), 4.27~4.29 (m, 2H), 6.11 (d, 2H), 6.36 (d, 1H), 6.41 (d, 2H), 6.83~6.90 (m, 6H), 6.94~6.97 (m, 2H), 7.13 (t, 1H), 7.38 (d, 1H), 7.51 (s, 1H), 8.43 (s, 1H).

[0080] The general formula of product T-1 in this example is as follows:

[0081] .

[0082] Preparation of Example 2 T-2

[0083] The preparation method of T-2 is as follows:

[0084] Step 1. Preparation of intermediate S-9: Add 25 g of S-1 into a 500 ml reaction flask, add 245 ml of DMF, lower the temperature to below 10 °C, protect with nitrogen, add 25 g of potassium tert-butoxide in batches. After completion, continue stirring for 1 h, then dropwise add 28 g of S-8. After the dropwise addition, raise the temperature to 25 °C and react for 5 h. The reaction equation of Step 1 is as follows:

[0085] ;

[0086] Post-treatment: Lower the temperature, then add 350 g of dichloromethane, add 400 g of water, perform liquid-liquid extraction, wash once with 400 g of saturated brine, then wash once with 300 g of 10% brine, add sodium sulfate for drying, add 70 g of alumina and stir for 1 h, then pass through a 140 g alumina chromatography column, elute with 150 g of DCM, evaporate the eluate to dryness to obtain 45 g of a green oily substance. Crystallize by stirring at low temperature with 40 g of dichloromethane and 40 g of petroleum ether, and filter to obtain the S-9 product with a yield of 70%;

[0087] Step 2. Preparation of intermediate S-10: Add 25 g of S-4 into a 500 ml reaction flask, add 250 ml of dichloromethane, add 9 g of S-9, and add 1 g of camphorsulfonic acid. Protect with nitrogen, raise the temperature to 50 °C and react for 5 h to obtain S-10. The reaction equation of Step 2 is as follows:

[0088] ;

[0089] Without purification, directly use it as the raw material for the next step. Due to impurity, the yield of this step is converted to 100%;

[0090] Step 3. Preparation of intermediate S-7: The same as the preparation step of S-7 in Example 1;

[0091] Step 4. Preparation of product P-2: Add 20 g of triethylamine to the reaction solution of S-10, protect with nitrogen, lower the temperature to 0 °C, and dropwise add the dichloromethane solution of S-7 (30.5 g of S-7 dissolved in 50 g of dichloromethane). After the dropwise addition, raise the temperature to 25 °C and react for 3 h. The reaction equation of Step 4 is as follows:

[0092] ;

[0093] Work-up: Directly pass the reaction solution through a silica gel chromatography column, then concentrate it. Next, dissolve the oily substance in 30 g of dichloromethane, add 300 g of methanol dropwise thereto, stir for crystallization, and filter with suction and dry to obtain 30.2 g of Product P-2 with a yield of 81%.

[0094] 1H NMR of Product T-2 in this example: δ 1.44~1.47 (m, 8H), 1.49~1.52 (m, 8H), 1.61~1.63 (m, 2H), 1.79~1.83 (m, 14H), 1.87~1.91 (m, 6H), 2.43~2.45 (m, 2H), 3.66~3.68 (m, 2H), 3.75~3.79 (m, 6H), 3.90~3.93 (m, 4H), 4.00~4.03 (m, 8H), 4.14~4.16 (m, 6H), 4.27~4.29 (m, 2H), 6.12 (d, 2H), 6.35 (d, 1H), 6.40 (d, 2H), 6.82~6.89 (m, 6), 6.94~6.96 (m, 2H), 7.14 (t, 1H), 7.37 (d, 1H), 7.50 (s, 1H), 8.42 (s, 1H).

[0095] The general formula of Product T-2 in this example is as follows:

[0096]

[0097] Example 3 Preparation of T-3

[0098] The preparation method of T-3 is as follows:

[0099] Step 1: Preparation of Intermediate S-12: Add 25 g of S-1 to a 500 ml reaction flask, add 245 ml of DMF, lower the temperature to below 10 °C, protect with nitrogen, add 25 g of potassium tert-butoxide in batches. After completion, continue stirring for 1 h, then add 28 g of S-11 dropwise. After the addition is complete, raise the temperature to 25 °C and react for 5 h; The reaction equation of Step 1 is as follows:

[0100] ;

[0101] Work-up: Lower the temperature, then add 350 g of dichloromethane, add 400 g of water, perform liquid-liquid extraction, wash once with 400 g of saturated brine, then wash once with 300 g of 10% brine, add sodium sulfate for drying, add 70 g of alumina and stir for 1 h, then pass through a 140 g alumina chromatography column, elute with 150 g of DCM, evaporate the eluate to obtain 45 g of a green oily substance. Stir the 45 g of the green oily substance with 40 g of dichloromethane and 40 g of petroleum ether at low temperature for crystallization, and filter with suction to obtain Product S-12 with a yield of 70%;

[0102] Step 2: Preparation of Intermediate S-13: Add 25 g of S-4 into a 500-ml reaction flask, add 250 ml of dichloromethane, add 9 g of S-12, and add 1 g of camphorsulfonic acid. Under nitrogen protection, heat up to 50 °C and react for 5 h to obtain S-13; the reaction equation for Step 2 is as follows:

[0103] ;

[0104] Without purification, it is directly used as the raw material for the next step. Due to its impurity, the yield of this step is converted to 100%;

[0105] Step 3: Preparation of Intermediate S-7: The preparation steps are the same as those for S-7 in Example 1;

[0106] Step 4: Preparation of Product P-2: Add 20 g of triethylamine to the reaction solution of S-13. Under nitrogen protection, lower the temperature to 0 °C, and dropwise add the dichloromethane solution of S-7 (30.5 g of S-7 dissolved in 50 g of dichloromethane). After the addition is complete, heat up to 25 °C and react for 3 h; the reaction equation for Step 4 is as follows:

[0107] ;

[0108] Work-up: Directly pass the reaction solution through a silica gel chromatography column, then concentrate it. Dissolve the oily substance with 30 g of dichloromethane, dropwise add 300 g of methanol to it, stir for crystallization, filter by suction and dry to obtain 26.4 g of Product P-3, with a yield of 73%.

[0109] The 1H NMR of Product T-2 in this example: δ 1.43~1.47 (m, 8H), 1.48~1.52 (m, 8H), 1.60~1.62 (m, 2H), 1.78 - 1.82 (m, 14H), 1.86~1.90 (m, 6H), 2.42~2.44 (m, 2H), 3.65~3.67 (m, 2H), 3.76~3.78 (m, 6H), 3.911 - 3.94 (m, 4H), 4.01~4.04 (m, 8H), 4.15~4.17 (m, 4H), 6.14 (d, 2H), 6.36 (d, 1H), 6.43 (d, 2H), 6.84~6.89 (m, 6H), 6.95~6.97 (m, 2H), 7.16 (t, 1H), 7.39 (d, 1H), 7.52 (s, 1H), 8.44 (s, 1H).

[0110] The general formula of Product T-3 in this example is as follows:

[0111] .

[0112] To evaluate its good reliability, we will compare it with the following three products, namely Compound B-1, B-2, and B-3, as comparative examples:

[0113] Comparative Example 1

[0114] Taking Compound B-1 as the comparison, the general formula of Compound B-1 is as follows:

[0115] 。

[0116] Comparative Example 2

[0117] Taking Compound B-2 as the comparison, the general formula of Compound B-2 is as follows:

[0118] 。

[0119] Comparative Example 3

[0120] Taking Compound B-3 as the comparison, the general formula of Compound B-3 is as follows:

[0121] 。

[0122] Application

[0123] In addition, a liquid crystal composition is provided as a matrix liquid crystal (M). This liquid crystal composition contains 50% of the compound (M-1) described in JP-A-2005-015473, 30% of the compound (M-2) described in JP-A-10-87565, and 20% of the compound (M-3) described in JP-T-2002-537280.

[0124] The general formula of Compound M-1 is as follows:

[0125] ;

[0126] The general formula of Compound M-2 is as follows:

[0127] ;

[0128] The general formula of Compound M-3 is as follows:

[0129] 。

[0130] The polyimide solution for the alignment film was coated on a glass substrate with a thickness of 0.7 mm and dried at 100 °C. After ten minutes, it was fired at 200 °C for 60 min to obtain a coating film. The obtained coating film was subjected to a rubbing treatment, and the rubbing treatment was carried out using a commercially available rubbing device to obtain a rubbed glass substrate.

[0131] In the host liquid crystal M, 40% by weight of the host liquid crystal M of the product compounds of Examples 1 to 3 and Comparative Examples 1 to 3 shown in Table 1, which are the compounds to be evaluated, were added to prepare a polymerizable compound composition. 1% of the photopolymerization initiator Irgacure 907 (manufactured by BASF), 0.1% of the polymerization inhibitor 4-methoxyphenol, and 80% of chloroform were added to prepare a coating solution; this coating solution was applied to a rubbed glass substrate by spin coating; after drying at 80°C for 1 min, it was further dried at 120°C for 1 min, and then irradiated with ultraviolet light at an intensity of 40 mW / cm 2 for 25 s using a high-pressure mercury lamp to produce the film to be evaluated. The films to be evaluated are Application Examples 1 to 6 shown in Table 1.

[0132] Orientation uniformity

[0133] For the obtained polymer, the degree of non-uniformity was evaluated by observation with a polarizing microscope. Ten films each containing the compound to be evaluated were prepared, and the number of non-uniformities was counted. The total number of non-uniformities observed in the ten films was summed up. If the number of non-uniformities was 0, it was recorded as excellent; if there was 1 non-uniformity, it was recorded as good; if there were 1 to 10 non-uniformities, it was recorded as medium; if there were more than ten non-uniformities, it was recorded as poor.

[0134] Humid heat durability

[0135] Regarding the test conditions for humid heat durability, a test was conducted for 500 hours in an environment of 85°C and 85% relative humidity. The Re(550) of the optical film before the test and the Re(550) of the optical film after the test were measured, and the humid heat durability was evaluated according to the following criteria.

[0136] A. The change amount between the Re(550) before the test and the Re(550) after the test is less than 10% of the Re(550) before the test.

[0137] B. The change amount between the Re(550) before the test and the Re(550) after the test is 10% or more and less than 30% of the Re(550) before the test.

[0138] C. The change amount between the Re(550) before the test and the Re(550) after the test is 30% or more of the Re(550) before the test.

[0139] Table 1

[0140]

[0141] As can be seen from Table 1, when the three compounds of Examples 1 to 3 and the three compounds of Comparative Examples 1 to 3 were subjected to temperature and humidity durability, the orientation was good, and the optical properties of Examples 1 to 3 and Comparative Examples 1 to 3 were all qualified; when testing the change value of Re(550), compared with the compounds of Comparative Examples 1 to 3, the three compounds of Examples 1 to 3 had higher temperature and humidity durability. Due to the presence of carbonate groups in the three compounds of Examples 1 to 3, when making the film, the degree of polymerization was higher and the stability was better, which could effectively improve the temperature and humidity durability.

[0142] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit and basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention.

[0143] In addition, it should be understood that although this specification is described according to embodiments, not every embodiment only contains an independent technical solution. This narrative way of the specification is only for clarity. Those skilled in the art should regard the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A polymerizable compound, characterized in that The polymerizable compound is a negative dispersion compound containing a carbonate group, and the negative dispersion compound containing a carbonate group is selected from the compounds represented by the general formula (1), (1); In the compound of the general formula (1), L1 and L2 each independently represent an alkylene group having 1 to 30 carbon atoms; one or more -CH2- in the alkylene group may be substituted by -O-; P1 represents a polymerizable group, and the polymerizable group P1 is selected from the group represented by the general formula P-1; , R3 represents a hydrogen atom.

2. A polymerizable compound according to claim 1, characterized in that The general formula (1) of the negative dispersion compound containing carbonate groups is selected from the general formula T-1, the general formula T-2 or the general formula T-3. The general formula T-1, the general formula T-2 and the general formula T-3 are as follows: T-1； T-2； T-3。 3. A polymerizable compound composition, characterized in that A polymerizable compound comprising the polymerizable compound of the general formula (1) according to claim 1 or 2 and at least one additional polymerizable compound.

4. A polymerizable compound composition according to claim 3, characterized in that: The additional polymerizable compound is selected from one or more compounds of Formula M-1, Formula M-2 or Formula M-3; Formula M-1, Formula M-2 or Formula M-3 is as follows: ； ； 。 5. An application of a polymerizable compound, characterized in that: The dispersion compound containing carbonate groups as described in claim 1 or 2 is used in negative dispersion optical film materials.

Images